Production of unsaturated nitriles



July 16, 1946.

ALIPHATIC ALDQXIME H. A. DUTCHER 2,404,280

PRODUCTION OF UNSATURATED NITRILES Filed Dec. 9, 1 943 UNSATURATEd NITRILE H o r 9 /4 DILUENT I I I T 1 a: CATALYTIC ,9 CONVERTER g 5 QUENCH E RECYCLE SATURATED 6 8 NITRILE INVENTOR I H. A DUTCHER AT ORNEYS( Patented July 16, 1946 2,404,280 PRODUCTION OF UN SATURATED NITRILES Harris A. Dutcher, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware Application December 9, 1943, Serial No. 513,568

' 9 Claims. (Cl. 260-464) This.v invention relates to the production of un saturated nitriles, More specifically it is concerned with the formation of acrylonitrile and its homologs by the simultaneous dehydration and dehydrogenation of aldehyde oximes.

The dehydration of aldehyde oximes to form saturated nitriles is a Well-known chemical reaction, usually accomplished, by treating the oximes with acetic anhydride' of acetyl chloride.

The formation of saturated nitriles among other.

products, by passing ketoximes over, thoria or alumina at 350-380 0., has been reported. (Mailhe and de Godon, Bull. soc. chim. 23, 18-30 (1918)) so far as I am aware, however, the formationof unsaturated nitriles by the simultaneous dehydration anddehydrogenation of aldehyde oximes. has notbeen accomplished hereto fore. 7 The object of my invention is toprovide a process for the production of unsaturated nitriles from. saturated aliphatic aldehyde oximes 1 ,A, further object of myinvention is to provide aprl'ocess for the production of acrylonitrile from propionaldehyde oxime, or a-fmethyl acrylonitrile from isobutyraldehyde oxime.

The process of my invention is carried out by passing the vapors of an. aliphatic saturated aldehyde oxime, for example, propionaldehyde 0X- ime, over a catalyst ofthe type which promotes both dehydration and dehydrogenation reactions, at a temperature in the dehydrogenation range. Catalysts comprising a major proportion of A0- tivated Alumina or bauxite and a minor proportion of the lower oxides of chromium, molybdenum, vanadium, or tungsten, are employed in my process. The preferred catalyst is composed of the mineral bauxite impregnated with a small per cent, say from 5 to 30%, of chromium sesquioxide, CmOs. Such catalysts are readily prepared in various ways well known to the art. The pressure in the catalyst zone may be varied over a rather wide range, typically from slightly below atmospheric to 50 pounds per sq. inugauge, but it is more convenient to operate at substantially atmospheric pressure. It is preferable to use a pressure just sufficiently above atmospheric. to maintain the desired flow rate. Low partial pressures of the reactants are advantageous. This may be attained by using an inert diluent gas such as steam or nitrogen.

The desired dehydration-dehydrogenation reaction may be carried out at temperatures within the range 700 to 1100 F. or even higher, however, a range of from 700 to 900 F. is generally preferred. The flow of reactant vapors through the catalyst. chamber is preferably maintainedat a rate such that an economical conversion per pass is obtained without an excessive amount of dehydrogenation or polymerization, A contact time ranging from 1 to 5 seconds isgenerallysatisfactory. Irisufliciently dehydrogenated products, such .as propionitrile, may be readily separated from the eifiuents and recycled, thereby increasing the ultimate yield of acrylonitrile. .Too severe-conditions may lead to the formation of the nitrile of propiolic acid, CHECCN.

Rapid. cooling of the reaction products is desirable, and in a preferred method of accomplishing this resultthe; efiluents are subjected to a direct Water quench, after which the acrylonitrile and other vproducts; .are: recovered by fractional distillation, v 1

The aldehyde oximes to .be employed in my process may be prepared: by any convenient method, such as the reaction of the aldehyde with hydroxylamine hydrochloride. The method of preparing the oximesis not a part of my invention. 1 The accompanying, drawing showsin schematic .form one specific embodiment of my invention.

An-aldehyde oxime, preferablyin admixture with asuitable diluentgas, is fed via line I into cata lytic converter Zwhere itcontacts a dehydratingdehydrogenating catalyst at a temperature f j from 700 to 900 F. The efiluents fromcatalytic converter 2 are conducted to quenching-means'ii where theyare quickly cooled preferably by waterto the temperature desired at the entrance toseparating means. 4, to which they are carriedby line 5. The aforementioned temperature-is, of

course, sufficiently below the reaction temperature that no further reactions take place. Sepa ration of the unsaturated nitrile from any saturated nitriles and other products may be readily accomplished by fractional distillation of the stream from quenching means 3. It is preferred to carry out. the dehydration-dehydrogenation under conditions such that excessive ,dehydrogen ation is avoided, even though this may result in the presence of some of the saturated nitrile in the efliuent from the catalyst chamber. This material may be readily recycled to the dehydrationv dehydrogenation zone, via line 6, if it is desired to increase the yield of unsaturated nitrile, The unsaturated nitrile is removed via line I, and any high boiling polymers or other by-products are withdrawn through line 8. Hydrogen gas is vented from the system through line 9 in the top of quenching means 3. I

range, quenching Example Propionaldehyde oxime, B. P. 130-132 C. was

ivaporized and passed continuously over a cata- Zlyst comprising principally bauxite with a minor prop0rtion of chromium sesquioxide, at a temperature of 800 F. The products were cooled by a direct water quench, acrylonitrile and pro jpionitrile being subsequently recovered and sep- 1 arated by fractional distillation. 1 was recycled to the catalyst chamber for further Propionitrile dehydrogenation. Acrylonitrile was obtained in good yield.

I claim:

l. The process of making acrylonitrile which" comprises passing the vapors of propionaldehyde oxime over a dehydrating-dehydrogenating cat- 0' alyst composed of chromium sesquioxide supvported on bauxite at a temperature of from 700 to 900 F;

2. The process of making a-methyl acrylonitrile which comprises passing the vapors of isobu- 3 tyraldehyde oxime over a dehydrating-dehydro- 1 genating" catalyst composed of chromium sesj quioxide supported on bauxite at a temperature 1 of from 700 to 900, F. r

3; The process of, making an aliphatic unsat- 1 uratednitrileof 3 to 4 carbon atoms per molecule 4 which comprises passingthe vapors of the corresponding aliphatic saturated aldehyde oxime over a dehydrating-dehydrogenating" catalyst composed of chromium sesquioxide supported on alumina at a temperature in the dehydrogenation 3 range, treating the reaction eflluentsto separately recover the unsaturated nitrile as the product ofthe process and the saturated nitrilecontained in said efiluents, and recycling said saturated nitrile to the catalytic conversion zone.

I 4. The process of making an aliphatic unsaturated-nitrile of 3 to 4 carbon atoms per molecule which comprises passing the vapors of the corresponding aliphatic saturated aldehyde oxime over a dehydrating-dehydrogenating catalyst com-t posed of v chromium sesquioxide supported on, alumina at a temperature in the dehydrogenation the reaction eflluentswith water:

to quickly cool same to a temperature at which any further reactions are prevented, and'fractionally distilling the resulting mixture to separately'recover the unsaturated nitrile as the product of the process and the saturated nitrile contained in said eflluents, and recycling said saturated nitrile to the catalytic conversion step.

, responding aliphatic saturated aldehyde at a temperature within the range of F. and at a pressure within the range of substan l a temperature within the range of 700 to 900 F. and at substantially atmospheric pres sure into contact with a catalyst composed of chromium sesquioxide' supported on bauxite effecting simultaneous dehydration and dehydrogenation of the aliphatic saturated aldehyde oxime to the corresponding aliphatic unsaturated nitrile.

7. The process of making an aliphatic unsaturated nitrile of 3 to 4 carbon atoms per molecule which comprises contacting the vaporsof the corresponding aliphatic saturated aldehyde oxime '700 to 900? tially atmospheric pressure to about pounds per square inch gage into contact with a catalyst composed of chromium sesquioxide supported on alumina for a period of time within the range'of 1 to '5 seconds such as to simultaneously dehydrate and dehydrogenate the aliphatic saturated aldehyde oxime to the corresponding aliphatic unsaturated nitrile. v

8. The process of making an'aliphaticiunsat urated nitrile of 3 to 4 carbon atoms per molecule which comprises contacting the vapors of 'th'efcorresponding saturated aliphatic aldehydel oxime with a dehydrating dehydrogenating catalyst comprising aluminum oxide and a minor proportion of a material selected from the groupconsi'st ing of the oxides of chromium; molybdenum; vanadium and tungsten at a temperature within the range of 700 to900fvF. therebyefie'cting conversion of the aliphatic saturated aldehyde oxime 5. The process of making analiphatic unsat- 7 urated nitrile of 3 to 4 carbon atoms per molecule 'to j the corresponding aliphatic unsaturated nitrile. V. g

9. The process of making an unsaturated nitrile which comprises contacting the vapors "of an aliphatic saturated aldehyde oxime over a dehydrating-dehydrogenating catalyst composed of aluminum oxide and a minor proportionjo'i a mal terial selected from the group consistingof the oxides of chromium, molybdenum, vanadium and tungsten at a temperature within the range of '700to 1 1O0F.' g

I r v HARRIS A, DUTCI lER. 

